Apparatus and methods using coatings for metal applications

ABSTRACT

An apparatus and methods for using coatings for metal applications are disclosed. According to one embodiment, an article comprises a cured polymeric film having a first reaction product of a cationic photoinitiator and a compound suitable for cationic polymerization. The article has a second reaction product of a free-radical photoinitiator and a compound suitable for free-radical polymerization; The article has a metal substrate, wherein the cured polymeric film coats the metal substrate.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of and priority to U.S.Provisional Application Ser. No. 62/770,006, entitled “APPARATUS ANDMETHODS USING COATINGS FOR METAL APPLICATIONS” filed Nov. 20, 2018,which is incorporated herein by reference in its entirety.

FIELD

The present application relates in general to metal coatings, and inparticular to an apparatus and methods for using coatings for metalapplications.

BACKGROUND

Solvent based coatings are utilized in the metal decorating industry dueto a number of properties imparted by their presence, includingmarring/scuff resistance, adhesion of decorative inks, enhancedformability and improved slip characteristics appropriate for subsequentforming operations. Particularly when forming metal substrates using adrawing process, the high slip characteristics and barrier functionalityof an applied coating allows for continuous processing of metal partswithout the damaging buildup of metal oxides on the tooling surfaces.

While solvent based coatings have the benefit of being cost effective(<$50/kg) as well as having good mechanical and chemical propertiesafter cure, the curing process releases solvent emissions that can bedetrimental to human and environmental health. Environmental regulationspertaining to solvent based coatings in certain localities has promotedthe development of “solvent-free” or one hundred percent solidsradiation curable formulations.

Radiation curable coatings have the benefit of instantaneous cure underambient conditions, low/zero emissions, good chemical resistance andhigh gloss characteristics. While some of the properties of radiationcurable coatings are attractive, the preferred crosslink density(acrylates per triglyceride) of greater than two, for these systems,combined with shrinkage upon cure can render the polymer brittleresulting in very poor elongation characteristics.

In order to improve the polymers elongation properties, a monofunctionalmonomer can be utilized reducing crosslink density. However, along withimproved elongation characteristics negative side effects such asincreased surface tack, reduced coating toughness, and in some cases alower glass transition temperature can result.

SUMMARY

An apparatus and methods for using coatings for metal applications aredisclosed. According to one embodiment, an article comprises a curedpolymeric film having a first reaction product of a cationicphotoinitiator and a compound suitable for cationic polymerization. Thearticle has a second reaction product of a free-radical photoinitiatorand a compound suitable for free-radical polymerization; The article hasa metal substrate, wherein the cured polymeric film coats the metalsubstrate.

The above and other preferred features, including various novel detailsof implementation and combination of elements, will now be moreparticularly described with reference to the accompanying drawings andpointed out in the claims. It will be understood that the particularmethods and apparatuses are shown by way of illustration only and not aslimitations. As will be understood by those skilled in the art, theprinciples and features explained herein may be employed in various andnumerous embodiments.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will become more apparent in view of the attacheddrawings and accompanying detailed description. The embodiments depictedtherein are provided by way of example, not by way of limitation,wherein like reference numerals/labels generally refer to the same orsimilar elements. In different drawings, the same or similar elementsmay be referenced using different reference numerals/labels, however.The drawings are not necessarily to scale, emphasis instead being placedupon illustrating aspects of the invention. In the drawings:

FIG. 1 shows a device used for application of the present coating, aflexographic coater, according to one embodiment.

FIG. 2 illustrates an exemplary system for applying a coating to coiledmetal, according to one embodiment.

FIG. 3 illustrates an exemplary system for applying a coating to a metalsheet, according to one embodiment.

FIGS. 4A and 4B illustrate exemplary systems for applying inks to ametal sheet, according to various embodiments.

FIG. 5 illustrates an exemplary coating layer build thin film UV curablecoating, according to one embodiment.

While the present disclosure is subject to various modifications andalternative forms, specific embodiments thereof have been shown by wayof example in the drawings and will herein be described in detail. Thepresent disclosure should be understood to not be limited to theparticular forms disclosed, but on the contrary, the intention is tocover all modifications, equivalents, and alternatives falling withinthe spirit and scope of the present disclosure.

DETAILED DESCRIPTION

An apparatus and methods for using coatings for metal applications aredisclosed. According to one embodiment, an article comprises a curedpolymeric film having a first reaction product of a cationicphotoinitiator and a compound suitable for cationic polymerization. Thearticle has a second reaction product of a free-radical photoinitiatorand a compound suitable for free-radical polymerization; The article hasa metal substrate, wherein the cured polymeric film coats the metalsubstrate.

The present apparatus and methods provide a radiation curable coatingcomposition consisting of both radical and cationic components havinggood elongation, good adhesion, a tack level low enough to avoidparticulate pickup as well as blocking, good marring resistance, and aglass transition temperature of greater than 40° C.

The present embodiments include applying a functional or functional anddecorative coating, or coating/ink combination to metal (e.g., a metalsheet, a metal coil) for deep drawing applications using coating and inkmaterial that contain little to no volatile organic compounds (VOC's).According to one embodiment, the present system and method includesapplying a coating, or coating/ink combination to both sides of aluminumsheet metal used for the manufacture of a deep-draw screw-caps forbeverage packaging applications. However, the coatings or coating andink combinations can be applied to any type of metal.

According to another embodiment, the coating system may be loaded withpigment, fillers including silica, bentonite, organoclays or anyadditive designed for rheology control with the end goal of forming anoffset ink using the coating system as a base. This offset ink has theadded advantage over other radiation curable systems of being printeddirect to metal and maintaining adhesion during forming operations aswell as passing a wedge bend test without failure.

The present coating protects metal substrates during the drawing processand could be optionally further decorated after the drawing process.

One embodiment includes an interpenetrating network or semiinterpenetrating network of a flexible cycloaliphatic epoxy and a vinylether crosslinked with UV radiation. According to another embodiment,the composition contains either one or both radical and cationicphotoinitiators. According to another embodiment, the compositioncontains a polymeric polydimethylsiloxane surface additive.

According to another embodiment, the composition contains a wax as aslip, antiblocking, or anti marring agent. According to anotherembodiment, the composition contains silica as a rheology additive,antiblocking agent, or the like. According to another embodiment, thecomposition contains a monofunctional monomer, to reduce the viscosity,increase adhesion, or adjust the glass transition temperature and/orcrosslink density of the coating. According to another embodiment, thecomposition contains a thermoplastic co-binder as an adhesion promoteror enhancer of coating hardness.

The present disclosure describes an environmentally friendly metalcoating formulation that is curable by ultraviolet radiation andcontains zero volatile organic compounds. FIG. 1 depicts an aniloxroller that can be used to apply a coating described herein, e.g., aUV-cured composition described herein, with a film thickness derivedfrom an anilox volume between 2-12 bcm. FIG. 1 shows a device used forapplication of the present coating, a flexographic coater, according toone embodiment. In printing, anilox is a method used to provide ameasured amount of ink to a flexo printing plate. An anilox roll is ahard cylinder, usually constructed of a steel or aluminum core which iscoated by an industrial ceramic whose surface contains millions of veryfine dimples, known as cells.

The flexographic coater allows for precise film volume, and thereby athickness, to be applied with the use of an anilox roller 12. The aniloxroller 12 has precision cells laser engraved into the ceramic, with thecell density and volume determining the amount of liquid to betransferred. The doctor blade 10 above the anilox roller 12 plays anumber of roles including maintaining the coating in the reservoir aswell as scraping away excess liquid so that only a metered quantity isapplied with each rotation of the roll. The printing plate 14 isutilized on the printing cylinder 15 when designs or spot varnishes needto be applied, with only the raised segments of the plate maintainingcontact with the anilox roll 12 and allowing for liquid transfer fromthe anilox to the plate. The substrate 17 is pushed into direct contactwith the printing plate 14 by a pressure roller 19 on the substrate'sbackside. The force of the pressure roller 19 must be maintained at alevel appropriate for the type of substrate, roller durometer, etc. asincorrect roller pressure can cause printing defects including lack oftransfer to the substrate or reduced print quality from excessivepressure.

In another embodiment, the film is applied using any number ofcomparable coating technologies, including roll coating, offsetprinting, slot die coating, and spray coating, so long as the filmweight applied meets the precise performance requirements for thecoating. In one embodiment, this coating is applied at a weight ofbetween 0.10-0.90 milligrams per square centimeter—it has been foundwhen cationic or cationic/free radical hybrid photoinitiating systemsare utilized, thin films ranging between 0.10-0.90 mg/sq cm can be curedto percent conversions greater than 50% without the negative effect ofoxygen inhibition. The added benefit is that film cohesion can bemaintained while elongation and adhesion of the film maximized duringthe drawing process at the film weights described above. It has furtherbeen found that above and below the film weight range listed, thecoatings fail upon drawing either due to lack of coverage, adhesionfailure, or fracturing due to lack of flow. Stress fractures developedduring the drawing process can be visualized using a thermal treatmentpost draw, which will cause defects known as powdering, flaking, or anykind of surface roughness defect to worsen. Defects of this kind willprevent the uniform decoration of these metal substrates post drawing,which will render the articles unsaleable in most industries.

In another embodiment the thin film, zero VOC radiation curable coatingcan additionally be applied to a solvent based or water basedthermoplastic coating as an overprint varnish to protect any ink orcoating decorations that have been applied prior to drawing from bothmechanical abrasion as well as provide resistance to solvation by asolvent.

In another embodiment the thin film, zero VOC radiation curable coatingcan be applied in multiple layers, the first layer functioning as a sizecoating or primer, with the ability to adhere to the metal substrate andreceive a decorative ink or coating followed by the thin film, zero VOCradiation curable coating composition as an over print varnish. FIG. 5shows a typical build for this type of system.

In some embodiments, the compositions described herein are substantiallyfree of VOCs. As used herein, the term “substantially free” means lessthan 5%, alternatively less than 3%, alternatively less than 2%,alternatively less than 1%, alternatively less than 0.5%, alternativelyless than 0.25%, alternatively less than 0.1%, alternatively less than0.05%, alternatively less than 0.01%, alternatively less than 0.001%,and/or alternatively free of. As used herein, “free of” means 0%.

A typical chemical composition for this radiation curable formulationincludes at least one flexible cycloaliphatic epoxide crosslinked with avinyl ether as an interpenetrating network. A preferred embodimentincludes 4-hydroxybutyl vinyl ether or triethyleneglycol divinyl etheras the vinyl ether and Bis (3,4-epoxycyclohexylmethyl) adipate as thecycloaliphatic epoxide. Concentrations of between 5 and 30 percent arepreferable for the vinyl ether, and that even more preferablyconcentrations of 10-20 percent may be utilized.

Concentrations between 30 and 60 percent are preferred for thecycloaliphatic epoxide, depending on whether any acrylate functionalityis to be utilized with an interpenetrating polymer network (IPN).Acrylate functionality can be introduced into the IPN in the form ofhigh elongation urethane acrylates like Sartomer CN9071 and CN966J75, aswell as in the form of isobornyl acrylate. Both can be utilized toincrease elongation of the film as well as increase the film weight,with curing energy levels of greater than 200 mJ/cm². Caprolactone orpolycarbonate diols like Capa 2050, Placcel 205U, Placcel 220N, Placcel220 EC, or CD220PL can also enhance elongation, flexibility, and impactresistance of the film. When utilized at levels below 25 percent, thesecomponents improve certain properties of the IPN due to their ability toact as a chain transfer agent, and in particular polycarbonate diols canbe used to dramatically improve solvent resistance.

In yet another embodiment, the IPN can be initially cured using UVRadiation to form a film that behaves similar to a thermoplastic coatingdue to its average crosslink density of less than two, exceptionaladhesion to aluminum, and moderate hardness.

A dual cure approach with a latent thermal cure initiator can furtherimprove solvent resistance. One embodiment for this application is ablocked isocyanate, as these compounds show good pot lives, goodreactivity with hydroxyl compounds, and good solvent resistance aftercure.

During forming operations (e.g., deep draw operations) the coating canbe utilized in a low crosslink density state where the properties areadequate for protection of the aluminum substrate and the film retainsenough cohesion to be drawn at exceptionally high degrees (e.g., greaterthan 300%). Once the forming step is complete, the film can be thermallycured to achieve its final properties. Solvent resistance of greaterthan 25 acetone rubs and in some cases greater than 50 rubs can beachieved with 10 minutes of post thermal curing at 180 degrees Celsius.Alternatively a phenolic type crosslinker can be used in a similarfashion to achieve the same final properties after thermal cure of thecoating.

Photoinitiators for the radiation curable formulation include bothcationic and free radical initiators used in conjunction. According toone embodiment, a combination includes a sulfonium salt based cationicinitiator like Omnicat 320 (triaryl sulfonium salt in propylenecarbonate) alongside an alpha hydroxy ketone like Omnirad 1173(2-hydroxy-2-methyl-1-phenyl-propan-1-one) or alternatively a lowmigration alpha hydroxy ketone like Esacure one.

Additives can provide important enhancements to the thin film, radiationcurable IPN's chemical and mechanical properties including adhesionpromotion, intercoat adhesion, surface slip, marring resistance, andhardness. A typical additive for promotion of adhesion and improvementof film hardness is a thermoplastic co-binder like Addbond LTH orVariplus 3350 UV. Modification of surface slip and blocking resistancecan also be achieved using additives like waxes or polymeric silicones.A typical additive for improvement of these properties is BYK UV 3500 orMicroklear 295—a micronized polyethylene carnauba wax blend. Accordingto one embodiment, metal is coated with a low VOC (less than 5% bysolids weight) UV curable coating with elongation properties greaterthan 300%, hardness of greater than 8H pencil hardness, and completeabrasion resistance when subjected to 500 rubs with a Sutherland Rubtester. This coating is applied at with a film thickness derived from ananilox volume between 2-12 bcm as laid down by an anilox roller, such asthe roller 12 illustrated in FIG. 1 . Depending on the design of theprinting press, the anilox roll is either semi-submerged in the inkfountain, or comes into contact with a metering roller, which issemi-submerged in the ink fountain. In either instance, a thick layer oftypically viscous ink is deposited on the roller. A doctor blade is usedto scrape excess ink from the surface leaving just the measured amountof ink in the cells. The roll then rotates to contact with theflexographic printing plate which receives the ink from the cells fortransfer to the printed material.

According to one embodiment, there is between 10-30% hydroxyl functionalmonomers and/or caprolactones. These hydroxy functional groups can befurther crosslinked using a thermally cured blocked isocyanate.

Curing stages may be performed in a stepwise manner, with the UV curebeing completed prior to forming operations and the latent thermal curebeing carried out post forming.

A coating is applied to a metal substrate using a coil or a flat sheetcoater. FIG. 2 illustrates an exemplary system for applying a coatingdescribed herein, e.g., a UV-cured composition, to a metal substrate 20that is staged in coil form at the feed to the coil coater process 24,according to one embodiment. The metal substrate 20 is staged in coilform at the feed to the coil coater process 24. The metal substrate 20is unwound at an uncoiler 26 and passed to an entrance accumulator 28 toensure consistent feed into the coating process train. The uncoiledmetal substrate 20 is then passed to a pre-treatment station 30, wherethe metal's surface is cleaned, possibly treated to increase its surfaceenergy, and possibly coated with a tie-coating, such as a size or basecoat. If the metal was coated with a tie-coating, it is then dried at adrying station 32 before being sent to the coil coater 24. The coilcoater 24 includes a prime coater station 34 that applies the main coloror functional coating to the metal substrate. The color or functionalcoating on the metal substrate is then cured in a curing oven 36. Next,at a top coat station 38 of the coil coater 24, a top coat such as aprotective over-varnish is applied to the metal substrate, and is curedin a finish oven 40. The substrate then might enter a water quenchstation 42 to quickly cool the coated metal, before entering an exitaccumulator 44 that allows for continually re-coiling the coated metalat the proper tension and rewind speed.

The coating processes may apply multiple coating layers onto one or bothsides of the metal substrate in one or multiple passes. FIG. 3illustrates an exemplary system for applying a coating described herein,e.g., a UV-cured composition, to a metal sheet 50 in which metal sheets50 may be stored in a sheet or plate feeder 52, according to oneembodiment. As shown in FIG. 3 , metal sheets 50 may be stored in asheet or plate feeder 52. From the sheet feeder 52, each metal sheet 50is fed to a conveyor (not shown). The sheets may be treated to clean andincrease their surface energy (not shown) prior to coating applicationat the application roller 54. During the coating application, the sheetis supported underneath by a pressure roller 56. As shown in FIG. 3 ,the conveyor transfers the metal sheet to a base coater 58 operation,where the metal sheet 50 is fed between the application roller 54 andthe pressure roller 56. A coating tray 60 transfers coating material tothe application roller 54 using a series of rollers 62, and theapplication roller applies the coating to each metal sheet as it passes.After the coating material is applied at the base coater 58, the metalsheet 50 is sent into a wicket oven 64 that includes wickets 66 thathold and convey individual metal sheets through the oven at a specifiedrate. The coated metal sheets are heated, dried, and cooled in thewicket oven 64 at specified temperatures and are then transferred to asheet or plate stacker 68.

A coating is a liquid that may contain, but is not limited to, binders,pigments, dyes, or waxes applied to the interior and/or exterior of asubstrate (e.g., aluminum metal) for decorative, functional, ordecorative and functional purposes. The coating may be applied usingtechniques to completely cover the substrate, or it may be applied tospecifically cover selective parts of the substrate. These includetie-layer coatings, including clear and base—relatively low pigmentcontaining—coatings, applied to assist adhesion of subsequent coatingsto the metal, color coatings for decorative purposes and over-varnishcoatings to protect the color coats and printed artwork.

Coatings that are applied to the interior and exterior surfaces of ametal packaging component may have different functions depending on theapplication of the component. For example, an interior coating on ametal packaging component directly contacting the food product protectsthe metal from corrosion by the food contents and protects the food frommetal contamination. Interior coatings may also contain agents to aid inthe functionality of the finished products. For example, slip agents,such as waxes, may be used in the case of screw cap closures to reducethe torque required to remove the cap from a bottle. Exterior coatingsare applied for decoration, to protect the package or packagingcomponent against corrosion, and to protect the printed design frommarring or abrasion.

Ink is applied to a flat metal sheet either in direct contact with themetal or over a coating previously applied to the metal using asheet-fed offset lithography printer. FIGS. 4A and 4B illustrateexemplary systems for applying inks to a metal sheet using a sheet-fedoffset lithography printer. FIG. 4A depicts a system in which metalsheets 70 may be stored in a sheet or plate feeder 72. FIG. 4B depicts asystem in which metal sheets 100 are fed into an offset printingassembly between an impression cylinder 102 on one side and an offsetcylinder 104 on the opposite side of the metal sheet 100.

In one embodiment, offset printing consists of an inked image beingtransferred from a plate to a blanket and then transferred to themetal's printing surface. These systems may be used with a lithographicprocess, employing a hydrophobic ink, including ultraviolet curableinks, and water-based fountain solution applied to an image carrier. Theink is applied to the image carrier via rollers along with a fountainsolution. The non-printing area of the image carrier attracts thefountain solution that repels the ink keeping the non-printing areasink-free. Inks may be applied to the surface of cured coatings to addsolid color or decorative elements to the metal. These inks can then becured and protected by over-coating with a clear over-varnish coating.

As shown in FIG. 4A, metal sheets 70 may be stored in a sheet or platefeeder 72. From the sheet feeder 72, each metal sheet 70 is fed to aconveyor (not shown) and then to a lithograph coater 73. There may be ablanket cylinder 74 on one side of the conveyor and a pressure roller 76on the opposite side of the conveyor at the lithograph coater 73. Inkapplicators 77 transfer ink through a series of rollers to the blanketcylinder 74. As shown in FIG. 4A, the conveyor transfers the metal sheetto the lithograph coater 73, where the metal sheet 70 moves between theblanket cylinder 74 and the pressure roller 76, and the blanket cylinder74 applies the coating to each metal sheet as it passes by on theconveyor. After receiving the inked image at the lithograph coater 73,the metal sheet 50 may be sent to an over-varnish coater 78 thatincludes an application roller 80 and a pressure roller 82 on oppositesides of the conveyor. A varnish tray 84 storing over-varnish is appliedto the application roller 80 through a series of rollers 86, and theover-varnish is then applied to the metal sheets by way of theapplication roller 80. After receiving varnish, the coated metal sheetsare then sent to a wicket oven 88 that includes wickets 90 that thathold individual metal sheets. The coated metal sheets are dried in thewicket oven 88 and then transferred to a sheet or plate stacker 92.

As shown in the embodiment of FIG. 4B, metal sheets 100 are fed into anoffset printing assembly between an impression cylinder 102 on one sideand an offset cylinder 104 on the opposite side of the metal sheet 100.Additional rollers 106 may also be used to help feed the metal sheetthrough the printing assembly. Ink applicators 108 transfer ink througha series of rollers to a plate cylinder 110 as shown in FIG. 4B. A watertray 112 storing water (or composition including water) is applied tothe plate cylinder 110 through a series of rollers 114. From the platecylinder 110, the ink is transferred to the offset cylinder 104. Whenthe metal sheet 100 is between the impression cylinder 102 and theoffset cylinder 104, the offset cylinder 104 applies the ink coating tothe metal sheet 100 as it passes through the offset printing assembly.As with the above embodiment described in FIG. 4A, the metal sheetincluding the inked image may be sent to an over-varnish coater, and maythen be sent to an oven for curing.

FIG. 5 illustrates an exemplary coating layer build thin film UV curablecoating, in which a thin film UV coating is applied directly onaluminum, followed by an ink or decorative coating and another thin filmUV coating, according to one embodiment. A thin film UV coating isapplied directly on aluminum, followed by an ink or decorative coatingand another thin film UV coating.

Additional embodiments as contemplated herein include the following:

In an embodiment, described herein is an article, comprising: a curedpolymeric film having a first reaction product of a cationicphotoinitiator and a compound suitable for cationic polymerization, anda second reaction product of a free-radical photoinitiator and acompound suitable for free-radical polymerization; and a metalsubstrate, wherein the cured polymeric film coats the metal substrate.

In some embodiments, the cured polymeric film is substantially free of avolatile organic compound. In some embodiments, the cured polymeric filmhas an average thickness derived from an anilox volume between 2-12 bcm.In some embodiments, the compound suitable for cationic polymerizationis a multifunctional epoxide. In some embodiments, the multifunctionalepoxide is a cycloaliphatic epoxide. In some embodiments, thecycloaliphatic epoxide is bis (3,4-epoxycyclohexylmethyl) adipate. Insome embodiments, the cycloaliphatic epoxide is incorporated into thefirst reaction product in an amount from 30% to 60% by weight based onthe total weight of the polymeric film. In some embodiments, thecompound suitable for free-radical polymerization is a vinyl ether. Insome embodiments, the vinyl ether is incorporated into the secondreaction product in an amount from 5 percent to 30 percent by weightbased on the total weight of the polymeric film. In some embodiments,the vinyl ether is selected from 4-hydroxybutyl vinyl ether andtriethyleneglycol divinyl ether. In some embodiments, the polymeric filmcomprises an interpenetrating network or semi-interpenetrating network.In some embodiments, the first reaction product and second reactionproduct are crosslinked. In some embodiments, the polymeric film furthercomprises a third reaction product comprising a free-radicalphotoinitiator and a second compound suitable for free-radicalpolymerization, and optionally an oligomer. In some embodiments, thesecond compound suitable for free-radical polymerization is isobornylacrylate or ethoxylated (9) trimethylol propane triacrylate andoptionally the oligomer is selected from the group consisting ofSartomer CN9071 and CN966J75. In some embodiments, the polymeric filmfurther comprises a fourth reaction product of a cationicphotoinitiator, a compound suitable for cationic polymerization, and apolycarbonate diol or caprolactone diol. In some embodiments, thecaprolactone diol or polycarbonate diol is incorporated into the fourthreaction product in an amount less than 25 percent by weight based onthe total weight of the polymeric film. In some embodiments, the articleis in the form of a sheet. In some embodiments, the article is in theform of a coil. In some embodiments, the article is in the form of ascrew-cap. In some embodiments, the article further comprises an inkcoated on the surface of the metal or polymeric film. In someembodiments, the ink comprises one or more components selected from thegroup consisting of a pigment, a filler such as bentonite, organoclays,and other additives designed for rheology control. In some embodiments,the ink directly contacts the metal. In some embodiments, the inkcontacts the polymeric film and does not contact the metal. In someembodiments, the ink is coated by the polymeric film. In someembodiments, the ink is coated by an over-varnish. In some embodiments,the cured polymeric film has an elongation of greater than 300%. In someembodiments, the cured polymeric film has a solvent resistance ofgreater than 25 solvent rubs or greater than 50 solvent rubs. In someembodiments, the cured polymeric film has complete scuff and marresistance when subjected to 500 rubs.

In one embodiment, described herein is a method, comprising: curing acomposition having a cationic photoinitiator and a monomer, afree-radical photoinitiator, a monomer and/or oligomer suitable forfree-radical polymerization with ultraviolet radiation forming aUV-cured composition; curing with a thermal cure initiator onto a metalsubstrate; and thermally activating the thermal cure initiator in theUV-cured composition to finalize the forming of the polymeric film. Insome embodiments, the method further comprises subjecting the article todeep drawing. In some embodiments, the method further comprisesdecorating the polymeric film with an ink. In some embodiments, thethermal curing agent is a blocked isocyanate.

In an embodiment, also described herein is a method, comprising: curingan ink composition having a cationic photoinitiator and a monomer, and afree-radical photoinitiator and a monomer and/or oligomer suitable forfree-radical polymerization with ultraviolet radiation forming aUV-cured composition; curing with a thermal cure initiator onto a metalsubstrate forming an ink-printed metal substrate; coating theink-printed metal substrate with the UV-cured composition; and thermallyactivating the thermal cure initiator in the UV-cured composition toform the polymeric film. In some embodiments, the thermal curing agentis a blocked isocyanate. In some embodiments, the method furthercomprises subjecting the article to deep drawing. In some embodiments,the method further comprises printing the polymeric film coated metalwith an ink.

Other Embodiments

In the claims articles such as “a,” “an,” and “the” may mean one or morethan one unless indicated to the contrary or otherwise evident from thecontext. Claims or descriptions that include “or” between one or moremembers of a group are considered satisfied if one, more than one, orall of the group members are present in, employed in, or otherwiserelevant to a given product or process unless indicated to the contraryor otherwise evident from the context. The invention includesembodiments in which exactly one member of the group is present in,employed in, or otherwise relevant to a given product or process. Theinvention includes embodiments in which more than one, or all of thegroup members are present in, employed in, or otherwise relevant to agiven product or process.

Furthermore, the invention encompasses all variations, combinations, andpermutations in which one or more limitations, elements, clauses, anddescriptive terms from one or more of the listed claims is introducedinto another claim. For example, any claim that is dependent on anotherclaim can be modified to include one or more limitations found in anyother claim that is dependent on the same base claim. Where elements arepresented as lists, e.g., in Markush group format, each subgroup of theelements is also disclosed, and any element(s) can be removed from thegroup. It should it be understood that, in general, where the invention,or aspects of the invention, is/are referred to as comprising particularelements and/or features, certain embodiments of the invention oraspects of the invention consist, or consist essentially of, suchelements and/or features. For purposes of simplicity, those embodimentshave not been specifically set forth in haec verba herein. It is alsonoted that the terms “comprising” and “containing” are intended to beopen and permits the inclusion of additional elements or steps. Whereranges are given, endpoints are included. Furthermore, unless otherwiseindicated or otherwise evident from the context and understanding of oneof ordinary skill in the art, values that are expressed as ranges canassume any specific value or sub—range within the stated ranges indifferent embodiments of the invention, to the tenth of the unit of thelower limit of the range, unless the context clearly dictates otherwise.

This application refers to various issued patents, published patentapplications, journal articles, and other publications, all of which areincorporated herein by reference. If there is a conflict between any ofthe incorporated references and the instant specification, thespecification shall control. In addition, any particular embodiment ofthe present invention that falls within the prior art may be explicitlyexcluded from any one or more of the claims. Because such embodimentsare deemed to be known to one of ordinary skill in the art, they may beexcluded even if the exclusion is not set forth explicitly herein. Anyparticular embodiment of the invention can be excluded from any claim,for any reason, whether or not related to the existence of prior art.

Those skilled in the art will recognize or be able to ascertain using nomore than routine experimentation many equivalents to the specificembodiments described herein. The scope of the present embodimentsdescribed herein is not intended to be limited to the above Description,but rather is as set forth in the appended claims. Those of ordinaryskill in the art will appreciate that various changes and modificationsto this description may be made without departing from the spirit orscope of the present invention, as defined in the following claims.

What is claimed is:
 1. A deep drawn article, comprising: a curedpolymeric film having a first reaction product of a cationicphotoinitiator and (3,4-epoxycyclohexylmethyl) adipate, a secondreaction product of a free-radical photoinitiator and a vinyl etherselected from 4-hydroxybutyl vinyl ether and triethyleneglycol divinylether, and a third reaction product of a hydroxyl functional monomer anda thermal curing agent; and a metal substrate, wherein the curedpolymeric film coats the metal substrate, and wherein the metalsubstrate and the cured polymeric film have been deep drawn, wherein thebis (3,4-epoxycyclohexylmethyl) adipate is incorporated into the firstreaction product in an amount from 30% to 60% by weight based on thetotal weight of the polymeric film and the vinyl ether is incorporatedinto the second reaction product in an amount from 5 percent to 30percent by weight based on the total weight of the polymeric film. 2.The article of claim 1, wherein the cured polymeric film issubstantially free of a volatile organic compound.
 3. The article ofclaim 1, wherein the cured polymeric film has an average thicknessderived from an anilox volume between 2-12 bcm.
 4. The article of claim1, wherein the polymeric film comprises an interpenetrating network orsemi-interpenetrating network.
 5. The article of claim 1, wherein thefirst reaction product and second reaction product are crosslinked. 6.The article of claim 1, wherein the polymeric film further comprises afourth reaction product comprising a free-radical photoinitiator and asecond compound suitable for free-radical polymerization, and optionallyan oligomer.
 7. The article of claim 6, wherein the second compoundsuitable for free-radical polymerization is isobornyl acrylate orethoxylated (9) trimethylol propane triacrylate and optionally theoligomer is a urethane acrylate.
 8. The article of claim 1, wherein thepolymeric film further comprises a fifth reaction product of a cationicphotoinitiator, a compound suitable for cationic polymerization, and apolycarbonate diol or caprolactone diol.
 9. The article of claim 8,wherein the caprolactone diol or polycarbonate diol is incorporated intothe fifth reaction product in an amount less than 25 percent by weightbased on the total weight of the polymeric film.
 10. The article ofclaim 1, in the form of a screw-cap.
 11. The article of claim 1, furthercomprising an ink coated on the surface of the metal or polymeric film.12. The article of claim 11, wherein the ink comprises one or morecomponents selected from the group comprising a pigment, a filler,organoclays, and other additives designed for rheology control.
 13. Thearticle of claim 11, wherein the ink directly contacts the metal. 14.The article of claim 11, wherein the ink contacts the polymeric film anddoes not contact the metal.
 15. The article of claim 11, wherein the inkis coated by the polymeric film.
 16. The article of claim 11, whereinthe ink is coated by an over-varnish.
 17. The article of claim 1,wherein the thermal curing agent is a blocked isocyanate.
 18. Thearticle of claim 1, wherein the cured polymeric film has a weight ofbetween 0.10-0.90 mg/sq cm.
 19. The article of claim 1, wherein thethird reaction product was formed after the metal substrate and thecured polymeric film were deep drawn.